New fluorinated alkoxy imines and their n-chloro- and n-bromo-derivatives, and process for their preparation

ABSTRACT

The present invention relates to novel fluorinated alkoxyimines having the formula: 
     
         R.sub.x --CF═N--O--CZ.sub.1 Z.sub.2 --CF.sub.3         (I) 
    
     wherein: 
     R x  is either F or a perhalogenated alkyl group containing from 1 to 3 carbon atoms, and 
     Z 1  and Z 2 , either equal to, or different from, each other, are F, Cl, Br, H or a perfluorinated alkyl group containing from 1 to 3 carbon atoms. 
     They are prepared by reacting a fluorinated alkoxyamine haivng the formula: 
     
         R.sub.x --CF.sub.2 --NH--O--CZ.sub.1 Z.sub.2 --CF.sub.3    (V) 
    
     with KF at a temperature comprised within the range of from 0° C. to 100° C. 
     The present invention relates furthermore to the N-chloro- and N-bromo-derivatives of said fluorinated alkoxyimines (I), which derivatives have the formulae: 
     
         R.sub.x --CF.sub.2 --NCl--O--CZ.sub.1 Z.sub.2 CF.sub.3     (VII) 
    
     and 
     
         R.sub.x --CF.sub.2 --NBr--O--CZ.sub.1 Z.sub.2 --CF.sub.3   (VIII).

This is a divisional of co-pending application Ser. No. 07/388,406 filedAug. 2, 1989, now abandoned.

The present invention relates to new fluorinated alkoxy imines, and to aprocess for their preparation. It relates also to new N-chloro andN-bromo-derivatives of the above said alkoxyimines, and to theirpreparation.

An object of the present invention is to provide new fluorinatedalkoxyimines.

Another object is to provide new N-chloro- and N-bromo-derivatives ofsaid fluorinated alkoxyimines.

A further object is to provide a process for the preparation of said newfluorinated alkoxyimines.

Still another object is to provide a process for preparing the N-chloro;N-bromo-, and N-fluoro-derivatives of said fluorinated alkoxyimines.

According to the first object of the present invention, a new class isprovided of fluorinated alkoxyimines having the formula:

    R.sub.X --CF═N--O--CZ.sub.1 Z.sub.2 --CF.sub.3         (I)

wherein:

R_(X) is either F or a perhalogenated alkyl group containing from 1 to 3carbon atoms, and Z₁ and Z₂, either equal to, or different from, eachother, are F, Cl, Br, H or a perfluorinated alkyl group containing from1 to 3 carbon atoms.

R_(x) is preferably either F or a perfluorinated alkyl group containingfrom 1 to 3 carbon atoms.

The preferred fluorinated alkoxy-imines belong to the class of formula

    CF.sub.2 ═N--O--CFZ--CF.sub.3                          (I')

wherein Z represents F, Cl or H.

The following compounds belong to class (I'):

    a) CF.sub.2 ═N--O--CF.sub.2 -CF.sub.3                  (II)

(pentafluoroethoxy)-carbonimide difluoride

    b) CF.sub.2 ═N--O--CFCl--CF.sub.3                      (III)

(1-chloro-1,2,2,2-tetrafluoroethoxy)-carbonimide difluoride

    c) CF.sub.2 ═N--O--CFH--CF.sub.3                       (IV)

(1,2,2,2-tetrafluoroethoxy)-carbonimide difluoride.

The starting compounds for preparing the fluorinated alkoxyimines (I)are the fluorinated alkoxy a mines having the formula:

    R.sub.x--CF.sub.2 --NH--O--CZ.sub.1 Z.sub.2 --CF.sub.3     (V)

The fluorinated alkoxy a mines (V), and a process for preparing them aredisclosed in a co-pending patent application by the same Applicant.

According to said process, a fluorinated oxazetidine ##STR1## isreacted, at a temperature comprised within the range of from -80° C. to+300° C., with HF, in the presence of a Lewis acid, preferably AsF₅.

According to the process of the present invention, a fluorinatedalkoxyamine

    R.sub.x --CF.sub.2 --NH--O--CZ.sub.1 Z.sub.2 --CF.sub.3    (V)

is reacted with KF at a temperature comprised within the range of from0° C. to 100° C.

A dehydrofluorination reaction takes place, whereby a fluorinatedalkoxyimine (I) is produced.

The temperature is preferably comprised within the range of from 25° C.to 50° C.

The molar ratio of KF to the alkoxyamine (V) is commonly comprisedwithin the range of from 5 to 50, and preferably of from 5 to 15.

The reaction times are usually comprised within the range of from 0.5hours to 30 hours, and, more frequently, of from 0.5 hours to 1 hour.

The fluorinated alkoxyimines (I) can be converted into theircorresponding N-chloro-, N-bromo- and N-fluoro-derivative by anhalogenation reaction, which is disclosed in the following.

The obtained compounds are:

    R.sub.x --CF.sub.2 --NCl--O--CZ.sub.1 Z.sub.2 --CF.sub.3   (VII)

    R.sub.x --CF.sub.2 --NBr--O--CZ.sub.1 Z.sub.2 --CF.sub.3   (VIII)

    R.sub.x --CF.sub.2 --NF--O--CZ.sub.1 Z.sub.2 --CF.sub.3    (IX)

The compounds of classes (VII) and (VIII) are new, and are a furtherobject of the present invention.

The preferred compounds belonging to classes (VII) and (VIII) are:

    CF.sub.3 --NCl--O--CFZ--CF.sub.3                           (VII')

    CF.sub.3 --NBr--O--CFZ--CF.sub.3                           (VIII')

wherein Z stays for F, Cl or H.

To the class (VII') the following compounds belong:

    a') CF.sub.3 --NCl--O--CF.sub.2 CF.sub.3                   (X)

(1,1,1-trifluoro-N-chloro-N-(pentafluoroethoxy)-methane-amine

    b') CF.sub.3 --NCl--O--CFClCF.sub.3                        (XI)

(1,1,1-trifluoro-N-chloro-N-(1-chloro-1,2,2,2-tetrafluoroethoxy)-methane-amine

    c') CF.sub.3 --NCl--O--CFHCF.sub.3                         (XII)

(1,1,1-trifluoro-N-chloro-N-(1,2,2,2-tetrafluoroethoxy)-methane-amine

To the class (VIII') the following compounds belong:

    a") CF.sub.3 --NBr--O--CF.sub.2 CF.sub.3                   (XIII)

(1,1,1-trifluoro-N-bromo-N-(pentafluoroethoxy)-methane-amine

    b") CF.sub.3 --NBr--O--CFClCF.sub.3                        (XIV)

(1,1,1-trifluoro-N-bromo-N-(1-chloro-1,2,2,2-tetrafluoroethoxy)-methane-amine

    c") CF.sub.3 --NBr--O--CFHCF.sub.3                         (XV)

(1,1,1-trifluoro-N-bromo-N-(1,2,2,2-tetrafluoroethoxy)-methane-amine.

The fluorinated alkoxyimines (I) are useful as monomers; they are alsouseful intermediate products for the preparation of their N-chloro-,N-bromo- and N-fluoro-derivatives.

The N-chloro-derivatives (VII), and the N-bromo-derivatives (VIII) areuseful as telogens. The N-fluoro-derivatives (IX) are useful ascatalysts for C₂ F₄ polymerization.

The fluorinated alkoxyimines (I) can be chlorofluorinated to yield theircorresponding N-chloro-derivatives, as follows: a fluorinatedalkoxyimine having the formula:

    R.sub.x --CF═N--O--CZ.sub.1 Z.sub.2 --CF.sub.3         (I)

is reacted with ClF at a temperature comprised within the range of from-160° C. to +25° C. The reaction can be carried out in the presence of acatalyst, which is constituted by a fluoride of an alkali metal, or ofan alkali-earth metal.

The catalyst is preferably constituted by CsF, RbF or KF, and, stillmore preferably, by CsF.

The preferred reaction temperature is usually comprised within the rangeof from -100° C. to +25° C.

The molar ratio of ClF to the alkoxyimine (I) is usually comprisedwithin the range of from 1 to 2 and, still more usually, within therange of from 1,0 to 1,2.

The molar ratio of the catalyst, computed as CsF, to the alkoxyimine (I)is commonly comprised within the range of from 0.5 to 100, and, stillmore commonly, within the range of from 5 to 10.

The fluorinated alkoxyimines (I) can be bromofluorinated to yield theircorresponding N-bromo-derivatives as follows: a fluorinated alkoxyiminehaving the formula:

    R.sub.x --CF═N--O--CZ.sub.1 Z.sub.2 --CF.sub.3         (I)

is reacted at a temperature comprised within the range of from -60° C.to +30° C. with Br₂ and a fluoride of an alkali metal or of analkali-earth metal.

The preferred reaction temperature is usually comprised within the rangeof from 0° C. to 30° C.

The metal fluoride is preferably constituted by CsF, RbF or KF, or, morepreferably, by CsF.

The molar ratio of Br₂ to the alkoxyimine (I) is usually comprisedwithin the range of from 1 to 100, and, still more usually, within therange of from 3 to 10.

The molar ratio of the metal fluoride, computed as CsF, to thealkoxyimine (I) is usually comprised within the range of from 2 to 100,and, still more usually, within the range of from 10 to 20.

EXAMPLES

The fluorinated alkoxyimines (I) can be fluorinated to yield theircorresponding N-fluoro-derivatives as follows: a fluorinated alkoxyiminehaving the formula:

    R.sub.x --CF═N--O--CZ.sub.1 Z.sub.2 --CF.sub.3         (I)

is reacted with F₂ at a temperature comprised within the range of from-196° C. to +25° C.

The reaction is optionally carried out in the presence of a catalystselected from the group consisting of the fluorides of the alkalimetals, and of the fluorides of the alkali-earth metals.

The preferred reaction temperature is usually comprised within the rangeof from -80° C. to +25° C.

The catalyst is preferably constituted by CsF, RbF or KF, and, stillmore preferably, by CsF.

The molar ratio of F₂ to the alkoxyimine (I) is usually comprised withinthe range of from 1 to 2 and, still more usually, within the range offrom 1,0 to 1,2.

The molar ratio of the catalyst, computed as CsF, to the alkoxy-imine(I) is commonly comprised within the range of from 0.5 to 100, and,still more usually within the range of from 5 to 10.

The above disclosed reactions of chlorofluorination, bromofluorinationand fluorination of the alkoxyimines (I) can be carried out in suitablesolvents compatible with the reactants and with the reaction products.

The following examples illustrate the inventive concept of the presentinvention.

EXAMPLE 1

This example describes the preparation of

    CF.sub.2 ═N--OCF.sub.2 --CF.sub.3

by starting from CF₃ --NH--OCF₂ --CF₃.

Potassium fluoride (Aldrich) was dried and activated by melting it in aplatinum crucible, and subsequently grinding it in a ball-mill under adry nitrogen atmosphere.

KF was stored, and weighed inside the reactor in a "dry box", filledwith nitrogen.

The reactor consisted of a Hoke 304 bomb of stainless steel of 75 ml ofcapacity, provided with a Nupro SS-4JBR valve. Then, inside the bomb KF(1.15 g, 19.8 mmol) was weighed in the "dry box", together with threesteel bearing balls.

To the reaction bomb, vacuum (5 microns Hg) was applied, and 2.70 mmolof

    CF.sub.3 --N(H)--OCF.sub.2 --CF.sub.3

was condensed under static vacuum conditions (5 microns Hg), by means ofa vacuum line of Pyrex glass, while the reaction bomb was kept at thetemperature of -196° C.

The reactor temperature was increased up to 24° C., and the reactor wasleft standing, with occasional shaking, for 16 hours. The volatilecontents of the bomb were then pumped inside an "U"-shaped trap, cooledwith liquid nitrogen, and were fractionated under dynamic vacuum (5microns Hg), through traps kept cooled at -50° C., -90° C., and -196°C.; inside the trap at -90° C., 2.49 mmol (yield 92.2%) of

    CF.sub.2 ═N--O--CF.sub.2 --CF.sub.3

was collected.

This compound was characterized by IR, ¹⁹ F-NMR and mass spectrum.

For the IR characterization, a Perkin-Elmer 1430 apparatus equipped witha 7500 data station was used. The spectra were obtained in the gas phasewith a 10-cm cell, provided with KCl windows attached with Halocarbon1500 wax.

For the N.M.R. characterization, an IBM NR 200AF apparatus was used,operating at 200.13 MHz for ¹ H and at 188.31 MHz for ¹⁹ F.

The downfield chemical shifts from internal (CH₃)₄ Si and CFCl₃respectiveli are reported as positive.

As regards the mass spectrum characterization a Hewlett-Packard 5985 Bapparatus, operating at 70 eV, was used. As the CI gas, CH₄ was used.The temperatures were measured with a thermocouple of J type.

The same characterization procedure was followed in Examples 2, 3, 4 and5.

IR (4 torr): 2785(vw), 2742(vw), 1969(vw), 1850(vw), 1755(v_(C)═N),vs),1394(sh,m), 1375(vs), 1237(vs), 1216(vs), 1195(s), 1108(vs), 1035(s),926(w), 848(m), 812(vw), 744(m), 726(sh,w), 645(w), 527(w) cm⁻¹ ;

wherein:

m=medium; sh=shoulder; w=weak; s=strong; vs=very strong; and vw=veryweak.

¹⁹ F-NMR F^(A) F^(X) C═N--OCF₂ ^(B) CF₃ ^(C) (CDCl₃, 24° C.) δA -54.4 (1F,br d), X -85.1 (1 F, br d), B -93.9 (2 F, d-q), C -84.8 ppm (3 F, t),J_(AX) =63.6, J_(BX) =2.6, J_(BC) =1.6, J_(AB) =J_(AC) =J_(CX) =0 Hz.

Mass spectrum major m/z (EI): 199 (M⁺), 180 (M-F⁺), 130 (CF₂ ═NOCF₂ ⁺),119 (CF₂ CF₃ ⁺), 69 (CF₃ ⁺), 64 (CF₂ ═N⁺), 50 (CF₂ ⁺), 47 (FCO⁺); majorm/z (CI): 200 (M+1⁺), 180 (M+1-HF⁺), 130 (CF₂ ═NOCF₂ ⁺), 119 (CF₃ CF₂⁺).

EXAMPLE 2

This example describes the preparation of

    CF.sub.2 ═N--OCFCl--CF.sub.3

by starting from CF₃ --NH--OCFCl--CF₃.

Potassium fluoride (Aldrich) was melted as received.

It was anyway stored, and weighed inside the reactor in a "dry box",filled with nitrogen.

The reactor consisted of a Hoke 304 bomb of stainless steel of 75 ml ofcapacity, provided with a Nupro SS-4JBR valve. Then, KF (2.25 g, 38.7mmol) was weighed inside the reactor in the "dry box", with two steelbearing balls of 3/8 inch of diameter being added.

To the bomb, vacuum (5 microns Hg) was then applied, and subsequently3.87 mmol of

    CF.sub.3 --N(H)--OCFCl--CF.sub.3

was added through a Pyrex vacuum line, under static vacuum conditions (5microns Hg), while the reactor was kept at the temperature of -196° C.

The temperature of the reaction bomb was increased up to 24° C., and thebomb was then placed inside an oil bath with stirring, at thetemperature of 60° C., for 12 hours; during this time period, thereactor was periodically withdrawn from the oil bath, in order to shakeit.

After allowing the reactor to cool down to 24° C., the volatile contentsof the bomb were subsequently pumped inside an "U"-shaped trap of Pyrex,cooled with liquid nitrogen, and were fractionated under dynamic vacuum(5 microns Hg), through a series of traps kept cooled at -70° C., -120°C., and -196° C.; inside the trap at -120° C.,

    CF.sub.2 ═N--OCFCl--CF.sub.3

was collected (2.12 mmol; yield 54.8%).

This compound was characterized as follows:

IR (4 torr): 2778(vw), 2742(vw), 1751(v_(C)═N,vs), 1375(vs), 1331(s),1286(sh,vw), 1231(vs), 1155(vs), 1098(vs), 1032(s), 998(vs), 946(vw),912(m), 863(vw), 828(w), 768(m), 727(m), 700(sh,w), 642(m), 606(vw),530(m) cm⁻¹ ;

¹⁹ F-NMR F^(A) F^(X) C═N--OCF₂ ^(B) ClCF₃ ^(C) (CDCl₃, 24° C.)δA -53.9(1 F,d-d), X -84.5 (1 F, br d), B -79.9 (1 F, q-t), C -83.2 ppm (3 F,d), J_(AX) =63.8, J_(AB) =J_(BX) =1.8, J_(BC) =3.0, J_(AC) =J_(CX) =0Hz.

Mass spectrum major m/z (EI): 215/217 (M⁺), 196/198 (M-F⁺), 180(M-Cl⁺),146/148 (M-CF₃ ⁺), 135/137 (CF₃ CFCl⁺), 130 (M-CF₂ Cl⁺), 85/87 (CF₂Cl⁺), 69 (CF₃ ⁺), 64 (CF₂ ═N⁺), 50 (CF₂ ⁺), 47 (COF⁺); major m/z (CI):216/218 (M+1⁺), 196/198 (M+1-HF⁺), 180 (M+1-HCl⁺), 146/148 (M-CF₃ ⁺),135/137 (CF₃ CFCl⁺), 130 (M-CF₂ Cl⁺).

EXAMPLE 3

This example describes the preparation of:

    CF.sub.2 ═N--OCHF--CF.sub.3

by starting from CF₃ --NH--OCHF--CF₃.

The preparation of CF₂ ═N--OCHF--CF₃ was carried out by exactly usingthe same operating procedure as previously adopted for CF₂═N--OCFCl--CF₃, with the following modifications:

CF₃ --N(H)--OCHF--CF₃ : 2.71 mmol

KF amount: 1.10 g (19.0 mmol)

Reaction time at 60° C.: 17 hours.

Fractionation: traps at -80° C., -120° C. and -196° C.

CF₂ ═N--OCHF--CF₃ (2.00 mmol) was collected inside the trap at -120° C.,with a yield of 73.8%.

CF₂ ═N--OCHF--CF₃ was characterized as follows:

IR (3 torr): 2998(v_(C-H),m), 1750(v_(C-N),vs), 1705(sh,vw), 1441(vw),1412(m), 1369(vs), 1329 (vw), 1290 (s), 1250(w), 1214(vs), 1192(vs),1143(vs), 1091(s), 1027(s), 961(m), 928 (vw), 903(vw), 872(m), 729(m),677(m), 637(w), 602(sh,vw), 584(sh,vw), 566(w), 534(w) cm⁻¹.

¹⁹ F-NMR F^(A) F^(X) C═N--OCHF^(B) CF₃ ^(D) (CDCl₃, 24° C.): ¹ H δ5,8(d-q-t), ¹⁹ F δA -56.1 (1 F,d-d), X -87.7 (1 F, br d), B -143.8 (1 F,d-q-d-d), D -82.4 ppm (3 F, d-d), J_(HA) =J_(HX) =0.6, J_(HB) =57.6,J_(HC) =3.2, J_(AX) =57.6, J_(AB) =3.0, J_(BX) =0.6, J_(BC) =6.1, J_(AC)=J_(CX) =0 Hz.

Mass spectrum: major m/z (EI): 181 (M⁺), 162 (M-F⁺), 112 (M-CF₃ ⁺), 101(CF₃ CHF⁺), 69 (CF₃ ⁺), 64 (CF₂ ═N⁺), 50 (CF₂ ⁺); major m/z (CI): 182(M+1⁺), 162 (M+1-HF⁺), 112 (M-CF₃ ⁺).

EXAMPLE 4

This example describes the preparation of

    CF.sub.3 --NCl--OCF.sub.2 CF.sub.3

by starting from CF₂ ═N--OCF₂ CF₃ and ClF.

The reactor consisted of a Hoke 304 bomb of stainless steel of 75 ml ofcapacity, equipped with a Nupro SS+4JBR valve.

To the bomb vacuum was applied (5 microns Hg) and the metal vacuum line,as well as the bomb, were treated with four successive portions of ClF₃gas (100 torr), with ClF₃ gas being added to the system under vacuum,and being let rest at the temperature of 22° C., each time for about 10minutes.

The bomb was evacuated and cooled down to -196° C., and 0.61 mmol of

    CF.sub.2 ═NOCF.sub.2 CF.sub.3

was condensed under static vacuum conditions (5 microns Hg);subsequently, 0.79 mmol of ClF was charged.

The temperature of the bomb was then allowed to slowly increase inside aDewar bottle, initially at -196° C. 9.5 hours later, the temperature wasof 15° C., and the bomb was removed from the Dewar bottle and was letstanding half an hour at the temperature of 22° C.

The reactor was then cooled down to -120° C., and any volatiles materialat this temperature was then removed under dynamic vacuum (5 micronsHg). The residual matter was then fractionated by pumping through aseries of cold traps kept cooled at the temperatures of -55° C., -100°C., and -196° C.

0.57 mmol (yield: 94%) of

    CF.sub.3 --N(Cl)OCF.sub.2 --CF.sub.3

was collected inside the separator at -100° C.

CF₃ --N(Cl)OCF₂ --CF₃ was characterized as follows:

IR (2 torr): 2047(vw), 1875(vw), 1392(m), 1276(vs), 1243(vs), 1218(s),1187(vs), 1097(vs), 953(w), 879(m), 853(w), 798(vw), 766(w), 741(m),693(vw), 672 (m), 523(w) cm⁻¹.

¹⁹ F-NMR CF₃ ^(C) N(Cl)--OCF^(A) F^(B) CF₃ ^(CD) (CDCl₃, 24° C.) δA-94.3, B -97.6 (2 F, rather broad typical AB) pattern, C -76.5 (3 F, t),D -84.8 ppm (3 F, t), J_(AB) =144, J_(AC) =J_(BC) =2.7, J_(AD) =J_(BD)=1.7, J_(CD) =0 Hz.

Mass spectrum major m/z (EI): 219 (M-Cl⁺), 131 (CF₂ ═NOCF₂ ⁺), 119 (CF₂CF₃ ⁺), 100 (CF₃ CF⁺), 99 (CF₃ NO⁺),

83 (CF₃ N⁺), 69 (CF₃ ⁺), 64 (CF₂ ═N⁺), 50 (CF₂ ⁺); major m/z (CI):254/256 (M+1⁺), 234/236 (M+1-HF⁺), 219 (M+1-Cl⁺), 218 (M+1-HCl⁺), 180(FCN--OC₂ F₅ ⁺), 135 (CF₃ CF₂ O⁺), 130 (CF₂ ═NOCF₂ ⁺), 119 (CF₃ CF₂).

EXAMPLE 5

This example describes the preparation of

    CF.sub.3 --NBr--OCF.sub.2 CF.sub.3

by starting from CF₂ ═N--OCF₂ CF₃, Br₂ and CsF.

Cesium fluoride (Cabot) was dried and activated by melting inside aplatinum crucible, followed by grinding inside a ball mill under a drynitrogen atmosphere; CsF was handled and weighed inside the reactor in anitrogen-filled "dry box".

Bromine (Fisher) was stored over P₄ O₁₀, inside a bulb provided with aglass/Teflon® stopcock.

The reactor was constituted by a bulb of 50 ml of capacity inside ascrew-top fitting ("Ace-Thred", Ace Glass Co.), which was tightly sealedby means of an O-ring compressed by a Teflon® insulating gasket, throughwhich a tube protruded, on which a glass/Teflon® stopcock was connected.

CsF (0.76 g, 5.0 mmol) was weighed inside the reactor in the "dry box",and a Teflon®-coated magnetic stirring bar was added.

The bulb was then put under vacuum (5 microns Hg, with the same vacuumbeing applied in all of the subsequent operating steps to be carriedunder vacuum), and 7.00 mmol of bromine was condensed by static vacuum,through a Pyrex vacuum line, with the reactor being maintained at thetemperature of -196° C. The CsF/Br₂ mixture was stirred at 22° C., for 4hours.

The reactor was cooled again with liquid nitrogen, and CF₂ ═N--OCF₂ CF₃(1.00 mmol) was added through the glass line, under static vacuum, byoperating in the dark. The reactor was heated to the temperature of 22°C., was wrapped inside an aluminum foil, and was kept 16 hours withstirring.

The volatile matters were then pumped into an "U"-shaped Pyrex trapcooled with liquid nitrogen. Ethylene (Matheson C.P., 3.00 mmol) wasallowed to condense inside the trap, under static vacuum. The liquidnitrogen bath was then removed from the trap (volume=73 ml), and thecontents of the trap were allowed to warm to 22° C., in order to causethe excess Br₂ to react. The resulting mixture, consisting of CF₃--N(Br)--OCF₂ CF₃, BrCH₂ CH₂ Br and unreacted CH₂ ═CH₂, was thenfractionated, under dynamic vacuum conditions, through a series of trapsat -55° C., -135° C. and -196° C., with the product CF₃ --N(Br)--OCF₂CF₃ (0.99 mmol, yield 99%) condensing inside the trap at -135° C.

CF₃ --N(Br)--OCF₂ CF₃ was characterized as follows:

IR (2 torr, cell with AgCl Plates): 1390(m), 1269(vs), 1241(vs),1214(s), 1184(vs), 1097(vs), 948(m), 876(m), 848(w), 754(m), 723(m),664(m), 634(vw), 520(vw) cm⁻¹.

¹⁹ F-NMR CF₃ ^(C) N(Br)--OCF^(A) F^(B) CF₃ ^(D) (CCl₄, (CD₃)₂ SO,coaxial, 24° C.): δA -95.4, B -98.9 (2 F, very broad typical AB pattern,A and B are the highest values of very broad peaks), C -75.1 (3 F, t), D-85.2 ppm (3 F, t), J_(AB) =not determined, J_(AC) =J_(BC) =3.0, J_(AD)=J_(BD) =1.6, J_(CD) =0. In order to determine the values of δ_(A),δ_(B) and J_(AB), a low-temperature spectrum was recorded in CDCl₃ at-30° C. The variable temperature unit was a Bruker B-VT 1000 with a"factor-specified" precision of ±0.5K.

Under these conditions, the N.M.R. spectrum is as follows: δA -94.8(d-q-q), B -99.3 (d), C -74.7 (d), D -84.9 ppm (t), J_(AB) =141.8,J_(AC) =5.1, J_(AB) =J_(BD) =1.4, J_(BC) =J_(CD) =0 Hz.

Although the invention has been described in conjunction with specificembodiments, it is evident that many alternatives and variations will beapparent to those skilled in the art in light of the foregoingdescription. Accordingly, the invention is intended to embrace all ofthe alternatives and variations that fall within the spirit and scope ofthe appended claims. The above references are hereby incorporated byreference.

Mass spectrum major m/z (EI): 297/299 (M⁺), 218 (M-BR⁺), 178/180 (CF₃═NBrO⁺), 164 (CF₃ NBr⁺), 130 (CF₃ NOCF⁺), 119 (CF₂ CF₃ ⁺), 79/81 (Br⁺),69 (CF₃ ⁺), 64 (CF₂ ═N⁺), 50 (CF₂ ⁺); 47 (COF⁺); major m/z (CI): 298/300(M+1⁺), 278/280 (M+1-HF⁺), 218 (M+1-HBr⁺), 164 (CF₃ NBr⁺), 199 (CF₃ CF₂⁺).

EXAMPLE 6

This example describes the preparation of

    CF.sub.3 --NF--OCF.sub.2 CF.sub.3

by starting from CF₂ ═N--OCF₂ CF₃ and F₂.

The reaction vessel was constituted by a Hoke bomb of stainless steelhaving a capacity of 150 ml, equipped with a Nupro SS-4JBR valve. To thebomb the vacuum of 5 microns Hg was applied (while the same vacuum valuewas applied throughout the subsequent operating steps to be carried outunder vacuum) and then 1 atm of F₂ was charged through a manifold ofstainless steel, in order to passivate the equipment.

After 3 hours at 22° C., F₂ was evacuated.

Then, before use, commercial F₂ (Air Products) was made flow through aan NaF scrubber.

The passivated bomb was cooled down to -196° C., and CF₂ ═N--OCF₂ CF₃(1.00 mmol) was condensed, by means of a static vacuum, through a vacuumline of Pyrex glass. The reaction was then put into communication withthe stainless steel line, and F₂ (1.05 mmol, a 5% excess) was added,still by operating at the temperature of liquid nitrogen.

The bomb was then placed inside a cold empty Derwar bottle, from whichliquid nitrogen had been removed short before; the upper end of theDewar bottle was covered with an aluminum foil The temperature of thereactor increased from -196° C. to 22° C. during a time period of about17 hours.

The reactor was then removed from the Dewar bottle, and was leftstanding at 23° C. for 6 hours.

The bomb was then cooled again with liquid nitrogen, and a trace ofvolatile matter was pumped off at -196° C.

Then, with the bomb being maintained at 23° C., the volatile contentswere pumped into an "U"-shaped Pyrex trap cooled with liquid nitrogen.The fractionation, under dynamic vacuum, through a series of trapscooled at -100° C., -135° C. and -196° C., supplied

    CF.sub.3 --N(F)--OCF.sub.2 CF.sub.3

(0.84 mmol, yield 84%) inside the trap at -135° C.

We claim:
 1. Fluorinated N-chloro-alkoxy-amines comprising the formula:

    R.sub.x --CF.sub.2 --NCl--O--CZ.sub.1 Z.sub.2 --CF.sub.3   (VII)

wherein: R_(x) is either F or a perhalogenated alkyl group containingfrom 1 to 3 carbon atoms, and Z₁ and Z₂, either equal to, or differentfrom, each other, are F, Cl, Br, H or a perfluorinated alkyl groupcontaining from 1 to 3 carbon atoms.
 2. FluorinatedN-chloroalkoxy-amines according to claim 1, wherein R_(x) is either F ora perfluorinated alkyl group containing from 1 to 3 carbon atoms. 3.Fluorinated N-chloro-alkoxy-amines according to claim 2, comprising theformula:

    CF.sub.3 --NCl--O--CFZ--CF.sub.3

wherein Z is F, Cl or H.
 4. Fluorinated N-bromo-alkoxy-amines comprisingthe formula:

    R.sub.x --CF.sub.2 --NBr--O--CZ.sub.1 Z.sub.2 --CF.sub.3   (VIII)

wherein: R_(x) is either F or a perhalogenated alkyl group containingfrom 1 to 3 carbon atoms, and Z₁ and Z₂, either equal to, or differentfrom, each other, are F, Cl, Br, H or a perfluorinated alkyl groupcontaining from 1 to 3 carbon atoms.
 5. Fluorinated N-bromo-alkoxyaminesaccording to claim 4, wherein R_(x) is either F or a perfluorinatedalkyl group containing from 1 to 3 carbon atoms.
 6. FluorinatedN-bromo-alkoxy-amines according to claim 5 comprising the formula:

    CF.sub.3 --NBr--O--CFZ--CF.sub.3

wherein Z is F, Cl or H.